CN102560116A - Method for recovering manganese and vanadium from titanium white waste acid, manganese slag and vanadium-containing steel slag - Google Patents
Method for recovering manganese and vanadium from titanium white waste acid, manganese slag and vanadium-containing steel slag Download PDFInfo
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- CN102560116A CN102560116A CN2011103526373A CN201110352637A CN102560116A CN 102560116 A CN102560116 A CN 102560116A CN 2011103526373 A CN2011103526373 A CN 2011103526373A CN 201110352637 A CN201110352637 A CN 201110352637A CN 102560116 A CN102560116 A CN 102560116A
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- titanium white
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- 239000011572 manganese Substances 0.000 title claims abstract description 84
- 229910052748 manganese Inorganic materials 0.000 title claims abstract description 79
- 229910052720 vanadium Inorganic materials 0.000 title claims abstract description 78
- LEONUFNNVUYDNQ-UHFFFAOYSA-N vanadium atom Chemical compound [V] LEONUFNNVUYDNQ-UHFFFAOYSA-N 0.000 title claims abstract description 78
- PWHULOQIROXLJO-UHFFFAOYSA-N Manganese Chemical compound [Mn] PWHULOQIROXLJO-UHFFFAOYSA-N 0.000 title claims abstract description 76
- 239000002893 slag Substances 0.000 title claims abstract description 75
- 239000002253 acid Substances 0.000 title claims abstract description 46
- 229910000831 Steel Inorganic materials 0.000 title claims abstract description 38
- 239000010959 steel Substances 0.000 title claims abstract description 38
- GWEVSGVZZGPLCZ-UHFFFAOYSA-N Titan oxide Chemical compound O=[Ti]=O GWEVSGVZZGPLCZ-UHFFFAOYSA-N 0.000 title claims abstract description 28
- 235000010215 titanium dioxide Nutrition 0.000 title claims abstract description 28
- 239000002699 waste material Substances 0.000 title claims abstract description 27
- 238000000034 method Methods 0.000 title claims abstract description 24
- 239000011575 calcium Substances 0.000 claims abstract description 29
- 229910052791 calcium Inorganic materials 0.000 claims abstract description 29
- 238000006243 chemical reaction Methods 0.000 claims abstract description 24
- OYPRJOBELJOOCE-UHFFFAOYSA-N Calcium Chemical compound [Ca] OYPRJOBELJOOCE-UHFFFAOYSA-N 0.000 claims abstract description 23
- 238000011084 recovery Methods 0.000 claims abstract description 7
- OSGAYBCDTDRGGQ-UHFFFAOYSA-L calcium sulfate Chemical compound [Ca+2].[O-]S([O-])(=O)=O OSGAYBCDTDRGGQ-UHFFFAOYSA-L 0.000 claims description 30
- XEEYBQQBJWHFJM-UHFFFAOYSA-N iron Substances [Fe] XEEYBQQBJWHFJM-UHFFFAOYSA-N 0.000 claims description 29
- WPBNNNQJVZRUHP-UHFFFAOYSA-L manganese(2+);methyl n-[[2-(methoxycarbonylcarbamothioylamino)phenyl]carbamothioyl]carbamate;n-[2-(sulfidocarbothioylamino)ethyl]carbamodithioate Chemical compound [Mn+2].[S-]C(=S)NCCNC([S-])=S.COC(=O)NC(=S)NC1=CC=CC=C1NC(=S)NC(=O)OC WPBNNNQJVZRUHP-UHFFFAOYSA-L 0.000 claims description 29
- 238000001914 filtration Methods 0.000 claims description 26
- CWYNVVGOOAEACU-UHFFFAOYSA-N Fe2+ Chemical compound [Fe+2] CWYNVVGOOAEACU-UHFFFAOYSA-N 0.000 claims description 24
- 239000007788 liquid Substances 0.000 claims description 18
- 239000000243 solution Substances 0.000 claims description 16
- 229910052742 iron Inorganic materials 0.000 claims description 15
- 239000000203 mixture Substances 0.000 claims description 14
- 238000005554 pickling Methods 0.000 claims description 13
- 239000012141 concentrate Substances 0.000 claims description 12
- 238000004062 sedimentation Methods 0.000 claims description 12
- VTLYFUHAOXGGBS-UHFFFAOYSA-N Fe3+ Chemical compound [Fe+3] VTLYFUHAOXGGBS-UHFFFAOYSA-N 0.000 claims description 10
- JEIPFZHSYJVQDO-UHFFFAOYSA-N iron(III) oxide Inorganic materials O=[Fe]O[Fe]=O JEIPFZHSYJVQDO-UHFFFAOYSA-N 0.000 claims description 10
- HEMHJVSKTPXQMS-UHFFFAOYSA-M Sodium hydroxide Chemical compound [OH-].[Na+] HEMHJVSKTPXQMS-UHFFFAOYSA-M 0.000 claims description 9
- 230000035484 reaction time Effects 0.000 claims description 7
- NLXLAEXVIDQMFP-UHFFFAOYSA-N Ammonia chloride Chemical compound [NH4+].[Cl-] NLXLAEXVIDQMFP-UHFFFAOYSA-N 0.000 claims description 6
- ODINCKMPIJJUCX-UHFFFAOYSA-N Calcium oxide Chemical compound [Ca]=O ODINCKMPIJJUCX-UHFFFAOYSA-N 0.000 claims description 6
- 230000007935 neutral effect Effects 0.000 claims description 6
- 238000000926 separation method Methods 0.000 claims description 5
- 229910052710 silicon Inorganic materials 0.000 claims description 5
- 229910052782 aluminium Inorganic materials 0.000 claims description 4
- 230000003647 oxidation Effects 0.000 claims description 4
- 238000007254 oxidation reaction Methods 0.000 claims description 4
- 239000012670 alkaline solution Substances 0.000 claims description 3
- 235000019270 ammonium chloride Nutrition 0.000 claims description 3
- QVGXLLKOCUKJST-UHFFFAOYSA-N atomic oxygen Chemical compound [O] QVGXLLKOCUKJST-UHFFFAOYSA-N 0.000 claims description 3
- UNTBPXHCXVWYOI-UHFFFAOYSA-O azanium;oxido(dioxo)vanadium Chemical compound [NH4+].[O-][V](=O)=O UNTBPXHCXVWYOI-UHFFFAOYSA-O 0.000 claims description 3
- 239000000292 calcium oxide Substances 0.000 claims description 3
- 235000012255 calcium oxide Nutrition 0.000 claims description 3
- 238000012423 maintenance Methods 0.000 claims description 3
- 230000001590 oxidative effect Effects 0.000 claims description 3
- 229910052760 oxygen Inorganic materials 0.000 claims description 3
- 239000001301 oxygen Substances 0.000 claims description 3
- 235000021110 pickles Nutrition 0.000 claims description 3
- 239000002244 precipitate Substances 0.000 claims description 3
- 239000007787 solid Substances 0.000 claims description 3
- 239000000376 reactant Substances 0.000 claims description 2
- 238000002386 leaching Methods 0.000 abstract description 12
- 238000005516 engineering process Methods 0.000 abstract description 5
- 238000000605 extraction Methods 0.000 abstract description 5
- 238000011161 development Methods 0.000 abstract description 2
- 239000000284 extract Substances 0.000 abstract description 2
- 238000003912 environmental pollution Methods 0.000 abstract 1
- NINIDFKCEFEMDL-UHFFFAOYSA-N Sulfur Chemical compound [S] NINIDFKCEFEMDL-UHFFFAOYSA-N 0.000 description 11
- 239000005864 Sulphur Substances 0.000 description 7
- 238000012545 processing Methods 0.000 description 5
- QAOWNCQODCNURD-UHFFFAOYSA-N Sulfuric acid Chemical compound OS(O)(=O)=O QAOWNCQODCNURD-UHFFFAOYSA-N 0.000 description 4
- 239000011593 sulfur Substances 0.000 description 4
- 229910052717 sulfur Inorganic materials 0.000 description 4
- 238000010586 diagram Methods 0.000 description 3
- VYPSYNLAJGMNEJ-UHFFFAOYSA-N Silicium dioxide Chemical compound O=[Si]=O VYPSYNLAJGMNEJ-UHFFFAOYSA-N 0.000 description 2
- XUIMIQQOPSSXEZ-UHFFFAOYSA-N Silicon Chemical compound [Si] XUIMIQQOPSSXEZ-UHFFFAOYSA-N 0.000 description 2
- ARZRWOQKELGYTN-UHFFFAOYSA-N [V].[Mn] Chemical compound [V].[Mn] ARZRWOQKELGYTN-UHFFFAOYSA-N 0.000 description 2
- 230000007613 environmental effect Effects 0.000 description 2
- 229910052751 metal Inorganic materials 0.000 description 2
- 239000002184 metal Substances 0.000 description 2
- 239000000047 product Substances 0.000 description 2
- 239000010703 silicon Substances 0.000 description 2
- 239000000126 substance Substances 0.000 description 2
- WKBOTKDWSSQWDR-UHFFFAOYSA-N Bromine atom Chemical compound [Br] WKBOTKDWSSQWDR-UHFFFAOYSA-N 0.000 description 1
- OKTJSMMVPCPJKN-UHFFFAOYSA-N Carbon Chemical compound [C] OKTJSMMVPCPJKN-UHFFFAOYSA-N 0.000 description 1
- ZAMOUSCENKQFHK-UHFFFAOYSA-N Chlorine atom Chemical compound [Cl] ZAMOUSCENKQFHK-UHFFFAOYSA-N 0.000 description 1
- 229910000616 Ferromanganese Inorganic materials 0.000 description 1
- OAICVXFJPJFONN-UHFFFAOYSA-N Phosphorus Chemical compound [P] OAICVXFJPJFONN-UHFFFAOYSA-N 0.000 description 1
- 238000003723 Smelting Methods 0.000 description 1
- SUAUKFMZICJTAY-UHFFFAOYSA-N [V].[Fe].[Mn] Chemical compound [V].[Fe].[Mn] SUAUKFMZICJTAY-UHFFFAOYSA-N 0.000 description 1
- 150000007513 acids Chemical class 0.000 description 1
- 238000005275 alloying Methods 0.000 description 1
- 239000004411 aluminium Substances 0.000 description 1
- XAGFODPZIPBFFR-UHFFFAOYSA-N aluminium Chemical compound [Al] XAGFODPZIPBFFR-UHFFFAOYSA-N 0.000 description 1
- 230000009286 beneficial effect Effects 0.000 description 1
- GDTBXPJZTBHREO-UHFFFAOYSA-N bromine Substances BrBr GDTBXPJZTBHREO-UHFFFAOYSA-N 0.000 description 1
- 229910052794 bromium Inorganic materials 0.000 description 1
- 239000004566 building material Substances 0.000 description 1
- 229910052799 carbon Inorganic materials 0.000 description 1
- 239000000460 chlorine Substances 0.000 description 1
- 229910052801 chlorine Inorganic materials 0.000 description 1
- 150000001875 compounds Chemical class 0.000 description 1
- 230000007123 defense Effects 0.000 description 1
- 230000002950 deficient Effects 0.000 description 1
- 235000003599 food sweetener Nutrition 0.000 description 1
- 239000011521 glass Substances 0.000 description 1
- 238000010438 heat treatment Methods 0.000 description 1
- 229910052500 inorganic mineral Inorganic materials 0.000 description 1
- DALUDRGQOYMVLD-UHFFFAOYSA-N iron manganese Chemical compound [Mn].[Fe] DALUDRGQOYMVLD-UHFFFAOYSA-N 0.000 description 1
- 239000004922 lacquer Substances 0.000 description 1
- 150000002696 manganese Chemical class 0.000 description 1
- 238000004519 manufacturing process Methods 0.000 description 1
- 239000000463 material Substances 0.000 description 1
- 150000002739 metals Chemical class 0.000 description 1
- 239000011707 mineral Substances 0.000 description 1
- 235000010755 mineral Nutrition 0.000 description 1
- 230000000737 periodic effect Effects 0.000 description 1
- 239000011574 phosphorus Substances 0.000 description 1
- 229910052698 phosphorus Inorganic materials 0.000 description 1
- 238000001556 precipitation Methods 0.000 description 1
- 239000002994 raw material Substances 0.000 description 1
- 238000011160 research Methods 0.000 description 1
- 239000000377 silicon dioxide Substances 0.000 description 1
- -1 soapmaking etc.) Substances 0.000 description 1
- 238000009628 steelmaking Methods 0.000 description 1
- 239000003765 sweetening agent Substances 0.000 description 1
- 239000001038 titanium pigment Substances 0.000 description 1
Images
Classifications
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- Y—GENERAL TAGGING OF NEW TECHNOLOGICAL DEVELOPMENTS; GENERAL TAGGING OF CROSS-SECTIONAL TECHNOLOGIES SPANNING OVER SEVERAL SECTIONS OF THE IPC; TECHNICAL SUBJECTS COVERED BY FORMER USPC CROSS-REFERENCE ART COLLECTIONS [XRACs] AND DIGESTS
- Y02—TECHNOLOGIES OR APPLICATIONS FOR MITIGATION OR ADAPTATION AGAINST CLIMATE CHANGE
- Y02P—CLIMATE CHANGE MITIGATION TECHNOLOGIES IN THE PRODUCTION OR PROCESSING OF GOODS
- Y02P10/00—Technologies related to metal processing
- Y02P10/20—Recycling
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- Manufacture And Refinement Of Metals (AREA)
- Processing Of Solid Wastes (AREA)
Abstract
The invention discloses a method for recovering manganese and vanadium from titanium white waste acid, manganese slag and vanadium-containing steel slag. Titanium white waste acid is used as acid leaching solution, leaching reaction is carried out on the acid leaching solution and manganese slag at the temperature of 90 ℃, the pH value of the acid leaching solution is adjusted by using vanadium-containing steel slag with high calcium content, and manganese and vanadium in the manganese slag, the vanadium-containing steel slag and the waste acid are recovered. The invention can recycle the waste acid and industrial harmful waste which pollute the environment, extract manganese in the manganese slag and the vanadium-containing steel slag, and recover vanadium in the waste acid and the vanadium-containing steel slag with the lowest cost and the highest recovery rate. Therefore, the method has the advantages of simple extraction process of manganese and vanadium, reduction of environmental pollution caused by acid liquor and harmful wastes, lower treatment cost than the known technology and development.
Description
Technical field
The present invention relates to reclaim the method for manganese, vanadium.It specifically is the method that from titanium white waste acid, manganese slag and v-bearing steel slag, reclaims manganese, vanadium.
Technical background
Manganese is seven races' element of period 4 in the periodic table of elements.At occurring in nature manganese II, III, IV and VII valence state are arranged, wherein common with II and IV valence state.Manganese is very easy to oxidation in air.Under heating condition, powdered manganese and chlorine, bromine, phosphorus, sulphur, silicon and carbon can chemical combination, at the known manganese-bearing mineral of occurring in nature kind more than 150 arranged approximately.In the industry, manganese and compound thereof are applied to the every field of national economy in modern times, and wherein Iron And Steel Industry is most important field, accounts for 90%～95% with the manganese amount, mainly as reductor and the sweetening agent in ironmaking and the steelmaking process, and are used for alloying.All the other manganese of 10%～5% are used for other industrial circle; Like chemical industry (making the various manganese salts that contain), light industry (being used for battery, match, seal lacquer, soapmaking etc.), building materials industry (tinting material and the decolourant of glass and pottery), national defense industry, electronic industry; And environment protection and husbandry, or the like.In a word, manganese has crucial strategic position in national economy.Have nothing in common with each other in the source of manganese slag, for example manganese ore is smelted the residue of back, or the useless scum silica frost of ferromanganese processing procedure or the like; Owing in the manganese slag, contain metals such as a large amount of silicon and aluminium, calcium, manganese, its composition Mn:10-20%, Al:5-10%, Ca:5-10%, Si:15-25%; Wherein about the about 10-20% of the content of manganese, have quite high recovery value, but owing to refine the manganese in the manganese slag; Excessively in wasting energy, cause energy loss in the processing procedure of convention, also or problems such as extraction yield is not high are arranged.It is can be by the mode of acceptances that the vitriol lixiviation method is carried manganese, but because sulfuric acid costs an arm and a leg, so be utilized in the technology that the manganese slag extracts manganese with spent acid, is worth by developmental research.
Generally adopt the spent acid of Titanium White Production By Sulfuric Acid Process institute output can consider to use in the world; This industry product per ton produces 4 tons of spent acid approximately; For many years to the processing of this part spent acid because processing cost is high, processing procedure is complicated, be the bottleneck of puzzlement white titanium pigment industry environment protection treating and enterprise development always.Contain S:100-250g/l, Fe:60-70g/l, Mn:2-4g/l, V:0.2-1g/l in the titanium white waste acid, wherein sulphur content therefore if utilize this spent acid, must be considered too high problem and the low excessively problem of pH value of sulfate radical up to more than the 100g/l.
V-bearing steel slag results from the smelting process of vanadium-bearing hot metal; Its characteristics are complicated component; Wherein the content with calcium and iron is the highest again, wherein contains part vanadium, manganese, and general common slag is formed V:0.5-3%, Fe:15-30%, Mn:2-5%, Ca:20-40%.Convention at present is quite a lot of to the manganese vanadium extraction method in the slag, but all because calcium contents is too high, the loss that calcium causes process manganese vanadium to extract easily.
Above-mentioned is the common method of order first three raw material convention, to such an extent as to but because defective separately can't satisfy the demand of technology.
Summary of the invention
The purpose of this invention is to provide a kind of method that from titanium white waste acid, manganese slag and v-bearing steel slag, reclaims manganese, vanadium.
The technical scheme that the present invention solves the problems of the technologies described above is following.
From titanium white waste acid, manganese slag and v-bearing steel slag, reclaim the method for manganese, vanadium, said titanium white waste acid is to produce the spent acid that contains high sulfate radical that produces in the titanium white process, and its composition is: S 100-250g/l, Fe60-70g/l, Mn 2-4g/l, V 0.2-1g/l; The composition weight percentage of said manganese slag is: Mn10-20%, Al 5-10%, Ca 5-10%, Si 15-25%; The composition weight percentage of said v-bearing steel slag is: V 0.5-3%, Fe 15-30%, Mn 2-5%, Ca 20-40%; With the titanium white waste acid is pickling liquor, under the condition of 90 ℃ of temperature, leaches reaction with the manganese slag, utilizes the v-bearing steel slag adjustment pickling liquor pH value with high calcium component, reclaims manganese, vanadium in manganese slag, v-bearing steel slag and the spent acid, and the concrete operations step is:
1. acidleach goes out: at first titanium white waste acid and manganese slag are placed reactor drum, temperature of reaction is 95 ℃, and adds v-bearing steel slag and regulate the pH value; Reaction times 1-5 hour; Calcium sulfate is separated out, and through filtering, separates and removes calcium sulfate; Obtain leach liquor, the weight ratio of each reactant is: manganese slag: titanium white waste acid: v-bearing steel slag=100: 3000-12000: 500-2000.
With the pH value of alkaline solution adjustment leach liquor between the 1-3, temperature maintenance is carried out the ferric reaction that settles out more than 95 ℃, after reaction is accomplished pickling liquor and ferric iron is filtered, separation obtains containing manganese, vanadium and ferrous pickling liquor except that ferric iron.
3. sedimentation vanadium; To contain manganese, vanadium and ferrous pickle liquor and carry out the reaction of sedimentation vanadium, with oxygen or air oxidation wherein vanadium and precipitate vanadium, after reaction is accomplished; Isolated by filtration; The surplus liquid that obtains containing a spot of ferrous solid vanadium concentrate and contain ferrous iron, manganese, isolate the vanadium concentrate after filtration after, obtain containing the surplus liquid of ferrous iron, manganese.
4. in the vanadium concentrate, add sodium hydroxide solution, make the vanadium dissolving in its vanadium concentrate, separate through filtration, obtain containing pure vanadium solution with a spot of ferrous iron.
5. the recovery of vanadium will contain vanadium solution and ammonium chloride reacts, and obtain ammonium meta-vanadate.
6. the recovery of manganese, contain the pH to 2-4 of surplus liquid of ferrous iron, manganese in the set-up procedure (3) after, it is scum that logical oxygenant makes ferrous iron become the ferric iron sedimentation; Behind the filtering scum, obtain manganese liquid, behind the pH to 4-6 of adjustment manganese liquid; Logical oxygenant makes manganese carry out oxidizing reaction, and sedimentation manganese slag, through filtering the manganese slag; Liquid after the filtration adds quicklime, obtains calcium sulfate and neutral solution, neutral solution is discharged after filtering out calcium sulfate.
The invention has the beneficial effects as follows:
1. utilize titanium white waste acid acidleach manganese slag among the present invention, utilize again that high-load calcium goes to adjust the pH value in the acidleach process in the v-bearing steel slag.This technology not only can be extracted the manganese in spent acid and manganese, the vanadium slag smoothly, also can the appropriateness of the vanadium in spent acid and the v-bearing steel slag be reclaimed.
2. the spent acid of the disposable contaminated solution environment of the present invention also can generate the calcium in the v-bearing steel slag calcium sulfate of environmental sound, is the inventive method of environmental protection, least cost.
Description of drawings
Fig. 1 is each composition variation diagram of the embodiment of the invention 1 different leaching times.
Fig. 2 is the embodiment of the invention 2 different each composition variation diagram of titanium white acid consumption.
Fig. 3 is the embodiment of the invention 3 each composition variation diagram of different v-bearing steel slag consumptions.
Embodiment
[one]
The manganese slag that 100 grams is contained manganese 11%, calcium 7%; Place reactor drum; At 90 ℃ of titanium white waste acids that add 6000g sulfur-bearing 200g/l, iron 70g/l, manganese 3g/l, vanadium 0.5g/l down; Be to contain vanadium with the 1000g composition in addition: calcium 2%: iron 40%: 15% v-bearing steel slag v-bearing steel slag adjustment pH value, the reaction times respectively is 1-5 hour; Detect to pickling liquor behind the filtering separation calcium sulfate.
Experimentize after reaction accomplishes with above-mentioned operational condition, the leaching result of gained manganese, iron, vanadium, calcium, sulphur is as shown in Figure 1.
Shown in Figure 1, be higher than 4 hours when the reaction times, the leaching yield of manganese, vanadium＞98%.Then only surplus about 1% residual, sulphur then can remove 66.5% to calcium.
[two]
The manganese slag that 100 grams is contained manganese 11%, calcium 7%; Place reactor drum; Reaction times respectively is 4 hours; Add the 3000-12000g sulfur-bearing down at 90 ℃: 200g/l, iron: 70g/l, manganese: 3g/l, vanadium: the 0.5g/l titanium white waste acid is to contain vanadium with the 1000g composition: calcium 2%: iron 40%, in addition: 15% v-bearing steel slag v-bearing steel slag adjustment pH value, detect to pickling liquor behind the filtering separation calcium sulfate.
With above-mentioned operational condition experimentize reaction after accomplishing the result that learnt as shown in Figure 2.
Find from Fig. 2 result, with condition like this, when leaching yield＞98% of titanium white acid manganese, vanadium during at＞6000g.Then only surplus 1.4% residual, sulphur then can remove 67.3% to calcium.But if increase titanium white acid, calcium fully becomes calcium sulfate precipitation with reaction of Salmon-Saxl; And sulphur content can increase thereupon.
[three]
The manganese slag that 100 grams is contained manganese 11%, calcium 7%; Place reactor drum; Reaction times respectively is 4 hours; Add the 6000g sulfur-bearing down at 90 ℃: 200g/l, iron: 70g/l, manganese: 3g/l, vanadium: the 0.5g/l titanium white waste acid is to contain vanadium with the 500-3000g composition: calcium 2%: iron 40%, in addition: 15% v-bearing steel slag v-bearing steel slag adjustment pH value, detect to pickling liquor behind the filtering separation calcium sulfate.With above-mentioned operational condition experimentize reaction after accomplishing the result that learnt as shown in Figure 3.
Find from Fig. 3, with condition like this, when leaching yield＞90% of v-bearing steel slag manganese, vanadium during at 500-2000g.But calcium also so thereupon increases, and sulphur changes after v-bearing steel slag＞2000g not quite.Therefore, if excessive increase v-bearing steel slag, the pH value when then significantly reducing acidleach cause leaching yield to descend, and calcium also increases.
[four]
1. the manganese slag that 100 grams is contained manganese 11%, calcium 7%; Place reactor drum; Add the 6000g sulfur-bearing down at 90 ℃: 200g/l, iron: 70g/l, manganese: 3g/l, vanadium: 0.5g/l titanium white waste acid; Be to contain vanadium with the 1000g composition in addition: calcium 2%: iron 40%: 15% v-bearing steel slag v-bearing steel slag adjustment pH value, the reaction times respectively is 4 hours, obtains acid leaching liquor.
2. remove ferric iron, between the 1-3, temperature maintenance is more than 95 ℃ with the pH value of alkaline solution adjustment acid leaching liquor; Carry out the ferric reaction that settles out; After reaction is accomplished pickling liquor and ferric iron are filtered, separate and remove ferric iron, obtain containing manganese, vanadium and ferrous pickling liquor.
3. sedimentation vanadium; To contain manganese, vanadium and ferrous pickle liquor and carry out the reaction of sedimentation vanadium, with oxygen or air oxidation wherein vanadium and precipitate vanadium, after reaction is accomplished; Isolated by filtration; The surplus liquid that obtains containing a spot of ferrous solid vanadium concentrate and contain ferrous iron, manganese, isolate the vanadium concentrate after filtration after, obtain containing the surplus liquid of ferrous iron, manganese.
4. in the vanadium concentrate, add sodium hydroxide solution, make the vanadium dissolving in its vanadium concentrate, separate through filtration, obtain containing pure vanadium solution with a spot of ferrous iron.
5. the recovery of vanadium will contain vanadium solution and ammonium chloride reacts, and obtain ammonium meta-vanadate.
6. after containing the pH to 2-4 of surplus liquid of ferrous iron, manganese in the set-up procedure (3), use oxygenant to make ferrous iron become the ferric iron sedimentation to be scum.Behind the filtering scum, obtain manganese liquid.Behind the pH to 4-6 of adjustment manganese liquid, logical oxygenant makes manganese carry out oxidizing reaction, and sedimentation manganese slag, through filtering the manganese slag.Liquid after the filtration adds quicklime, obtains calcium sulfate and neutral solution, neutral solution is discharged after filtering out calcium sulfate.
After the above operation, the extraction yield and the product purity of manganese, vanadium, iron are as shown in the table.
| ? | Manganese | Vanadium | Iron |
| Total extraction yield % | 90 | 90.2 | 95.1 |
| Purity % | 98.9 | 99.3 | 96.5 |
Claims (1)
1. from titanium white waste acid, manganese slag and v-bearing steel slag, reclaim the method for manganese, vanadium; It is characterized in that; Said titanium white waste acid is to produce the spent acid that contains high sulfate radical that produces in the titanium white process, and its composition is: S100-250g/l, Fe 60-70g/l, Mn 2-4g/l, V 0.2-1g/l; The composition weight percentage of said manganese slag is: Mn 10-20%, Al 5-10%, Ca 5-10%, Si 15-25%; The composition weight percentage of said v-bearing steel slag is: V 0.5-3%, Fe 15-30%, Mn 2-5%, Ca 20-40%; With the titanium white waste acid is pickling liquor, under the condition of 90 ℃ of temperature, leaches reaction with the manganese slag, utilizes the v-bearing steel slag adjustment pickling liquor pH value with high calcium component, reclaims manganese, vanadium in manganese slag, v-bearing steel slag and the spent acid, and the concrete operations step is:
(1) acidleach goes out: at first titanium white waste acid and manganese slag are placed reactor drum, temperature of reaction is 95 ℃, and adds v-bearing steel slag and regulate the pH value; Reaction times 1-5 hour; Calcium sulfate is separated out, and through filtering, separates and removes calcium sulfate; Obtain leach liquor, the weight ratio of each reactant is: manganese slag: titanium white waste acid: v-bearing steel slag=100: 3000-12000: 500-2000;
(2) with the pH value of alkaline solution adjustment leach liquor between the 1-3, temperature maintenance is carried out the ferric reaction that settles out more than 95 ℃, after reaction is accomplished pickling liquor and ferric iron is filtered, separation obtains containing manganese, vanadium and ferrous pickling liquor except that ferric iron;
(3) sedimentation vanadium; To contain manganese, vanadium and ferrous pickle liquor and carry out the reaction of sedimentation vanadium, with oxygen or air oxidation wherein vanadium and precipitate vanadium, after reaction is accomplished; Isolated by filtration; The surplus liquid that obtains containing a spot of ferrous solid vanadium concentrate and contain ferrous iron, manganese, isolate the vanadium concentrate after filtration after, obtain containing the surplus liquid of ferrous iron, manganese;
(4) in the vanadium concentrate, add sodium hydroxide solution, make the vanadium dissolving in its vanadium concentrate, separate through filtration, obtain containing pure vanadium solution with a spot of ferrous iron;
(5) recovery of vanadium will contain vanadium solution and ammonium chloride reacts, and obtain ammonium meta-vanadate;
(6) recovery of manganese, contain the pH to 2-4 of surplus liquid of ferrous iron, manganese in the set-up procedure (3) after, it is scum that logical oxygenant makes ferrous iron become the ferric iron sedimentation; Behind the filtering scum, obtain manganese liquid, behind the pH to 4-6 of adjustment manganese liquid; Logical oxygenant makes manganese carry out oxidizing reaction, and sedimentation manganese slag, through filtering the manganese slag; Liquid after the filtration adds quicklime, obtains calcium sulfate and neutral solution, neutral solution is discharged after filtering out calcium sulfate.
Applications Claiming Priority (2)
| Application Number | Priority Date | Filing Date | Title |
|---|---|---|---|
| TW100136758A TWI432584B (en) | 2011-10-11 | 2011-10-11 | A method for extracting metal from manganese residue |
| TW100136758 | 2011-10-11 |
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| Publication Number | Publication Date |
|---|---|
| CN102560116A true CN102560116A (en) | 2012-07-11 |
| CN102560116B CN102560116B (en) | 2013-08-14 |
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Cited By (7)
| Publication number | Priority date | Publication date | Assignee | Title |
|---|---|---|---|---|
| JP2016172682A (en) * | 2015-03-17 | 2016-09-29 | 住友大阪セメント株式会社 | Manufacturing method of gypsum and manufacturing method of cement composition |
| CN107541599A (en) * | 2017-10-27 | 2018-01-05 | 成都先进金属材料产业技术研究院有限公司 | Use the preparation method of acid high manganese high purity containing vanadium leachate vanadium |
| CN108359806A (en) * | 2018-04-09 | 2018-08-03 | 攀枝花市红杉钒制品有限公司 | A kind of integrated conduct method of slag, vanadium slag, titanium white waste acid |
| CN109576492A (en) * | 2018-04-03 | 2019-04-05 | 东北大学 | A method of using slag processing titanium white waste acid and extracting valuable constituent element |
| CN110304758A (en) * | 2019-06-20 | 2019-10-08 | 厦门大学 | A kind of method of manganese ion in removal Mn-bearing waste water |
| CN112176208A (en) * | 2020-10-29 | 2021-01-05 | 攀枝花市山青钒业有限公司 | Method for co-extracting vanadium and scandium by using titanium white waste acid and vanadium-containing high-calcium high-phosphorus slag |
| CN113165897A (en) * | 2018-10-10 | 2021-07-23 | 里克希维亚有限公司 | Compositions and methods for purifying metals from steelmaking waste streams |
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| Publication number | Priority date | Publication date | Assignee | Title |
|---|---|---|---|---|
| CN103641177B (en) * | 2013-12-03 | 2015-07-29 | 新奥科技发展有限公司 | A kind of method extracting high calcium slag mineral |
| CN111485102A (en) * | 2020-04-26 | 2020-08-04 | 张响 | Process for full-recycling titanium white waste acid |
Citations (2)
| Publication number | Priority date | Publication date | Assignee | Title |
|---|---|---|---|---|
| CN101177757A (en) * | 2007-11-22 | 2008-05-14 | 攀钢集团攀枝花钢铁研究院 | Alloying material for smelting vanadium-and manganese-containing alloy steel and preparation method thereof |
| CN101182600A (en) * | 2007-06-19 | 2008-05-21 | 昆明理工大学 | Combined technology for separating and extracting vanadium from high calcium and high ferro steel scoria |
-
2011
- 2011-10-11 TW TW100136758A patent/TWI432584B/en active
- 2011-11-01 CN CN2011103526373A patent/CN102560116B/en active Active
Patent Citations (2)
| Publication number | Priority date | Publication date | Assignee | Title |
|---|---|---|---|---|
| CN101182600A (en) * | 2007-06-19 | 2008-05-21 | 昆明理工大学 | Combined technology for separating and extracting vanadium from high calcium and high ferro steel scoria |
| CN101177757A (en) * | 2007-11-22 | 2008-05-14 | 攀钢集团攀枝花钢铁研究院 | Alloying material for smelting vanadium-and manganese-containing alloy steel and preparation method thereof |
Non-Patent Citations (2)
| Title |
|---|
| 付自碧等: "钛白废酸浸出钢渣提钒试验研究", 《钛工业进展》, vol. 26, no. 5, 31 October 2009 (2009-10-31), pages 33 - 37 * |
| 刘愚: "钛白废酸在黄铁矿参与下浸出软锰矿制取硫酸锰的研究", 《云南冶金》, vol. 27, 31 July 1998 (1998-07-31), pages 45 - 49 * |
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| JP2016172682A (en) * | 2015-03-17 | 2016-09-29 | 住友大阪セメント株式会社 | Manufacturing method of gypsum and manufacturing method of cement composition |
| CN105985037A (en) * | 2015-03-17 | 2016-10-05 | 住友大阪水泥株式会社 | Method of producing gypsum and method of producing cement composition |
| CN107541599A (en) * | 2017-10-27 | 2018-01-05 | 成都先进金属材料产业技术研究院有限公司 | Use the preparation method of acid high manganese high purity containing vanadium leachate vanadium |
| CN107541599B (en) * | 2017-10-27 | 2019-07-26 | 成都先进金属材料产业技术研究院有限公司 | Use the preparation method of acid high manganese high purity containing vanadium leachate vanadium |
| CN109576492A (en) * | 2018-04-03 | 2019-04-05 | 东北大学 | A method of using slag processing titanium white waste acid and extracting valuable constituent element |
| CN109576492B (en) * | 2018-04-03 | 2020-07-14 | 东北大学 | Method for treating titanium white waste acid and extracting valuable components by using steel slag |
| CN108359806A (en) * | 2018-04-09 | 2018-08-03 | 攀枝花市红杉钒制品有限公司 | A kind of integrated conduct method of slag, vanadium slag, titanium white waste acid |
| CN113165897A (en) * | 2018-10-10 | 2021-07-23 | 里克希维亚有限公司 | Compositions and methods for purifying metals from steelmaking waste streams |
| CN110304758A (en) * | 2019-06-20 | 2019-10-08 | 厦门大学 | A kind of method of manganese ion in removal Mn-bearing waste water |
| CN112176208A (en) * | 2020-10-29 | 2021-01-05 | 攀枝花市山青钒业有限公司 | Method for co-extracting vanadium and scandium by using titanium white waste acid and vanadium-containing high-calcium high-phosphorus slag |
| CN112176208B (en) * | 2020-10-29 | 2021-10-26 | 攀枝花市山青钒业有限公司 | Method for co-extracting vanadium and scandium by using titanium white waste acid and vanadium-containing high-calcium high-phosphorus slag |
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| Publication number | Publication date |
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| CN102560116B (en) | 2013-08-14 |
| TWI432584B (en) | 2014-04-01 |
| TW201315817A (en) | 2013-04-16 |
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